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Water : A green solvent with a difference... By  Balmukund Thakkar
Contents ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
Water : A solvent for chemical reactions ,[object Object],[object Object],[object Object],[object Object],[object Object]
Water : A green solvent ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
Water as a solvent with a difference ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
Structure of Water molecule ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
Hydrogen Bonding in Water ,[object Object],[object Object],[object Object]
Water as  dual activator  medium ,[object Object],[object Object],[object Object]
Water as  dual activator  medium ,[object Object],[object Object],Chankeshwara S. V., Rudrawar S., Chakraborti A. K.;  12th ISMAS-WS-2007, March 25-30, 2007, Cidade de Goa, Dona Paula, Goa
Forced hydrophobic interactions ,[object Object],[object Object],[object Object],[object Object],[object Object]
Forced hydrophobic interactions ,[object Object],[object Object]
Acceleration of Diels–Alder reaction in water : Pioneer example of Forced hydrophobic interactions ,[object Object],J. Am. Chem. Soc. ,  1980 ,  102 , 7816 Solvent Additional component Rate constant  K 2  X 10 5  M -1 S -1   Isooctane - 5.94 MeOH - 75.5 Water - 4400 ” LiCl (4.86 M) 10800 ” β -Cyclodextrin 10900 ” α -Cyclodextrin 2610 Solvent Additional component Rate constant  K 2  X 10 5  M -1 S -1   Isooctane - 796 MeOH - 666 Water - 22600 ” β -Cyclodextrin 13800
Solvation by water ,[object Object],[object Object],[object Object],[object Object]
Pericyclic reactions ,[object Object],Angew. Chem. Int. Ed.   2005 ,  44 , 3275 –3279 trans, trans -2,4-hexadienyl acetate N-propylmaleimide Solvent Conc. (M) Time (h) Yield (%) Toluene 1 144 79 Acetonitrile 1 >144  43 MeOH 1 48 82 Neat 3.7 10 82 Water 3.7 8 81
Pericyclic reactions ,[object Object],[object Object],[object Object],[object Object],J. Am. Chem. Soc ., 1999 ,  121 , 6798. J. Am. Chem. Soc.,   2000 ,  122 , 10418 3-phenyl-1-(2-pyridyl)-2-propen-1-one Solvent ee (%) Acetonitrile 17 THF 24 Ethanol 39 Chloroform 44 Water 74
Pericyclic reactions ,[object Object],Angew. Chem. Int. Ed. 2005, 44, 3275 –3279 Quadricyclane DMAD Solvent Conc. (M) Time (h) Toluene 2 >120 EtOAc 2 >120 Acetonitrile 2 84 DCM 2 72 Dimethyl sulfoxide 2 36 MeOH 2 18 Neat 4.5 48 D 2 O 4.5 3/4  (45 min) C 6 F 14 4.5 36 H 2 O 4.5 1/6  (10 min)
Pericyclic reactions ,[object Object],[object Object],Angew. Chem. Int. Ed.  2005 ,  44 , 3275 –3279 Naphthyl ether derivative Solvent Yield (%) Toluene 16 Acetonitrile 27 MeOH 56 DMF 21 Neat 73 H 2 O 100
Reactions of carbanion equivalents ,[object Object],[object Object],[object Object],J. Am. Chem. Soc .,  2003 ,  1 25 , 4062.
Reactions of carbanion equivalents ,[object Object],[object Object],[object Object],J. Am. Chem. Soc .,  2003 ,  125 , 2958 Solvent Amount (Equivalents) Time Yield %(α :  γ ) DMF 6 72 65 (0 : 100) THF 6 72 20 (0 : 100) DCM 6  24 None Ethanol 6 72 97 Neat 24 None H 2 O 2 ml 72 90 (0 : 100) H 2 O 6 24 85 (99 : 1)
[object Object],[object Object],Reactions of carbanion equivalents J. Am. Chem. Soc .,  2003 ,  125 , 2958
Reactions of carbocation equivalents ,[object Object],[object Object],[object Object],[object Object],Solvent Yield (%) H 2 O / THF  (1 : 4) 91 Dry THF 10
Reactions of carbocation equivalents ,[object Object],[object Object],[object Object],Catalysts / additives Yields (%) Sc(OTf) 3  / -- 3  Sc(OTf) 3  / surfactant (SDS) 88 Sc(DC) 3  / -- 92
Reactions of carbocation equivalents ,[object Object],[object Object],[object Object]
Reactions of carbocation equivalents ,[object Object],[object Object],[object Object],J. Am. Chem. Soc .,  2002 ,  124 , 11971
Reactions of carbocation equivalents ,[object Object],[object Object],[object Object],J. Am. Chem. Soc .,  2002 ,  124 , 11971
Reactions of radicals A.  Lactone formation :-  J. Am. Chem. Soc .,  2000 ,  122 , 11041 Solvent Yield (%) Hexane 0 Benzene 0 DCM 0 THF 0 Ethanol 3 Methanol 6 2,2,2-trifluoroethanol 18 Acetonitrile 13 DMF 13 Formamide 24 DMSO 37 H 2 O 78 Solvent Yield (%) Hexane (20 ml) 10 Benzene (100 ml) 23 MeOH (20 ml) 0 H 2 O (100 ml) 69 Solvent Yield Benzene 14 Water 70
Reactions of radicals ,[object Object],[object Object],[object Object],[object Object]
Multicomponent reactions ,[object Object],[object Object],Passerini reaction :- Ugi reaction :- β -lactam deri. synthesis :-  J. Am. Chem. Soc.  2004 ,  126 , 444
Conclusions ,[object Object],[object Object],[object Object],[object Object],[object Object]
References ,[object Object],[object Object],[object Object],[object Object]
Water : A Green Solvent With A Difference

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Water : A Green Solvent With A Difference

  • 1. Water : A green solvent with a difference... By Balmukund Thakkar
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  • 25.
  • 26. Reactions of radicals A. Lactone formation :- J. Am. Chem. Soc ., 2000 , 122 , 11041 Solvent Yield (%) Hexane 0 Benzene 0 DCM 0 THF 0 Ethanol 3 Methanol 6 2,2,2-trifluoroethanol 18 Acetonitrile 13 DMF 13 Formamide 24 DMSO 37 H 2 O 78 Solvent Yield (%) Hexane (20 ml) 10 Benzene (100 ml) 23 MeOH (20 ml) 0 H 2 O (100 ml) 69 Solvent Yield Benzene 14 Water 70
  • 27.
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